CN101634021B - Electroless gold plating solution - Google Patents
Electroless gold plating solution Download PDFInfo
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- CN101634021B CN101634021B CN2008101301265A CN200810130126A CN101634021B CN 101634021 B CN101634021 B CN 101634021B CN 2008101301265 A CN2008101301265 A CN 2008101301265A CN 200810130126 A CN200810130126 A CN 200810130126A CN 101634021 B CN101634021 B CN 101634021B
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Abstract
The invention provides an electroless gold plating solution, which comprises (i) a water-soluble gold cyanide compound; (ii) a complexing agent; (iii) at least one compound selected from pyridinium carboxylate compounds having phenyl or aralkyl. The electroless gold plating solution can form a gold-plated film with very strong adhesiveness and does not corrode substrate metal films such as nickel, copper, cobalt or palladium films and other films.
Description
Technical field
The present invention relates to electroless gold plating solution.The present invention further relates to the electroless gold plating solution (electroless gold plating solution) that can be used to deposited gold on the metallic surface of nickel or copper and so on.
Background technology
Conventional; Adopt gold-plated final surface treatment as the electronic industry parts; Said electronic industry parts are for example printed substrate, ceramic IC assembly, ITO plate and IC-card etc., and this is because electroconductibility, weldability, physical features such as hot crimping connectivity (connectivity by thermal crimp) and the oxidation-resistance that gold utensil has.For the major part in these electronic industry parts, preferably adopt electroless and do not adopt plating, this is because need carry out gold-plated to the electric individual components with complicated shape.
Printed substrate carries out electroless nickel plating usually on base metal (for example copper wiring) surface, often also on the surface of nickel, carry out Electroless plating.For this situation; Displacement (substitution) gold plating liquid and autocatalysis electroless gold plating solution are that people are well-known; Said immersion gold plating fluid power enough in the base metal of dissolving nickel and so on deposited gold, the effect deposited gold of the autocatalysis electroless gold plating solution can be through there being catalytic activity to gold utensil reductive agent.Immersion gold plating even when adopting the autocatalysis Electroless plating, also will utilize the immersion gold plating reaction through the replacement(metathesis)reaction deposited gold between gold and the base metal when causing the reaction of autocatalysis Electroless plating.In other words, at the autocatalysis electroless gold plating solution with after the plating object contacts, at once because the deposition of gold takes place the replacement(metathesis)reaction between base metal and the gold.The replacement(metathesis)reaction of said Electroless plating is utilized the motivating force of the dissolving of base metal as deposited gold.This replacement(metathesis)reaction is to carry out through the structure of the base metal of grain boundary etc. and so on, so the level of dissolution of base metal there are differences.Compared to other zone, the material that replacement(metathesis)reaction preferably occurs in grain boundary of base metal etc. and so on is more weak zone significantly, and in other words, the dissolving of base metal has produced discordance.The base metal corrosion that starts from the uneven dissolution of base metal can cause some problems, for example gold-plated film of gained and the adhesive local embrittlement of base metal and lower solder bonds intensity.
The immersion gold plating liquid that people have proposed to have cyanic acid also comprises ammonium chloride; Local corrosion (for example, referring to Japanese Unexamined Patent Application S59-6365) with the control base metal perhaps also comprises nitrogenous compound; For example the deposition of gold control agent (for example; Referring to Japanese Unexamined Patent Application 2000-144441), perhaps also comprise polymine (for example, Japanese Unexamined Patent Application 2003-13248).Yet, although these electroless gold plating solutions can reduce the corrosion as the nickel film of substrate metal layer to a certain extent, the problem that still exists gold-plated film sedimentation velocity to reduce, this is because the dissolution rate of nickel film reduces.
The objective of the invention is to address the above problem, a kind of electroless gold plating solution is provided, make it not cause under the base metal corrosive prerequisite the evenly tackiness of plating and raising and base metal.
Summary of the invention
In order to address the above problem, the inventor is through painstaking research, and discovery can be reached above-mentioned target through the electroless gold plating solution that use comprises the combination of specific components, thereby has accomplished the present invention.In other words, the present invention relates to a kind of electroless gold plating solution, it is used at the enterprising row metal plating of metallic surface, and this electroless gold plating solution comprises:
(i) water-soluble gold tricyanide compound;
(ii) complexing agent;
(iii) pyridine carboxylic acid class (pyridinium carboxylate) compound, it has phenyl or aralkyl at 1.
And, the invention provides a kind of electroless gold plating solution, it also comprises;
(iv) as at least a compound of base metal surfaces treatment agent, it is selected from formic acid and salt thereof, and hydrazine and verivate thereof.
And the present invention also provides a kind of being used on the metallic surface, to carry out gold-plated electroless gold plating solution, and it comprises:
(i) water-soluble gold tricyanide compound;
(ii) comprise at least a complexing agent that is selected from the ethylenediamine tetramethylene phosphonic acid or derivatives thereof;
(iii) at least a compound, it is selected from 1 pyridine carboxylic acid compounds with phenyl or aralkyl;
(iv) as at least a compound of base metal surfaces treatment agent, it is selected from hydrazine and verivate thereof;
(v) be selected from least a compound of poly carboxylic acid and salt thereof.
Embodiment
The electroless gold plating solution of the application of the invention, that can suppress base metal does not hope the dissolving that occurs, promptly corrosion can improve tackiness, can form uniform golden plated film, and can improve the sedimentation rate of gold.
And electroless gold plating solution of the present invention can deposit the golden film with good appearance and good solder bonds intensity, can not cause the base metal local corrosion of nickel and so on simultaneously.
It is bright to describe this law in detail below.Electroless gold plating solution of the present invention is a kind of aqueous solution that comprises following component: water-soluble gold tricyanide compound; Complexing agent; At 1 pyridine carboxylic acid compounds with phenyl or aralkyl, gather carboxyl salt and at least a base metal surfaces treatment agent also optional comprising; For example formic acid or its salt, perhaps hydrazine or derivatives thereof.
The water-soluble gold tricyanide compound that the present invention uses does not have special limitation, can be gold tricyanide compound arbitrarily, as long as this gold tricyanide compound is water-soluble, can gold ion be provided for plating liquid, and is usually used in gold plating liquid and gets final product.The example of this water-soluble gold tricyanide compound comprises the sour potassium of dicyan fund (I) and four cyano gold (III) sour potassium.Said water-soluble gold tricyanide compound can be independent kind, perhaps can be with two kinds or more kinds of mixing use.
Electroless gold plating solution of the present invention suitably comprises these water-soluble gold tricyanide compounds, and gold ion concentration is the 0.1-10 grams per liter, for example is preferably the 0.5-5 grams per liter.
Being used for complexing agent of the present invention can be the material that any known is used for gold plating liquid, as long as this material is water miscible, can gold ion stably be remained in the plating bath, and the plating bath that comprises this complexing agent can not dissolved nickel, cobalt or palladium basically and got final product.The example of these complexing agents comprises organic phospho acid or its salt that has a plurality of phosphonate groups or its salt in the molecule, and aminocarboxylic acid or its salt etc.Phosphonic acids or its salt preferably comprise the group shown in the for example following structure.
-PO3MM′
Wherein M and M ' can be identical or different, are selected from Wasserstoffatoms, sodium, potassium and ammonium.The quantity of phosphate group or its salt is 2-6 in the said compound, preferred 2-5.
Being used for organic phospho acid of the present invention is the compound with following structure.
Formula 1:
X wherein
1Be Wasserstoffatoms, C
1-C
5Alkyl, aryl, arylalkyl, amino, perhaps use-OH ,-COOM or PO
3The substituted C of MM '
1-C
5Alkyl.M and M ' define like preceding text.And m and n are integer, are 0 or 1.
Wherein, term " alkyl " comprises the alkyl with straight or branched." C
1-C
5Alkyl " expression comprises the alkyl of 1-5 carbon atom.C
1-C
5The example of alkyl is a methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec.-butyl, the tertiary butyl or amyl group etc.An example of aryl is a phenyl or naphthyl etc.An example of arylalkyl is to have above-mentioned aryl as substituent abovementioned alkyl.An amino example is the amino that has Wasserstoffatoms and abovementioned alkyl etc. on the nitrogen-atoms.
Formula 2:
X wherein
2For for example-CH
2-,-CH (OH)-,-C (CH
3) (OH)-,-CH (PO
3MM ')-,-C (CH
3) (PO
3MM ')-,-CH (CH (COOM)-or-C (CH
3) (COOM)-etc., M and M ' are as stated.
Formula 3:
X in the formula
3-X
7With above-mentioned X
1Similar.Yet, X
3-X
7In at least two be-PO3MM '.
The example of above-mentioned organic phospho acid comprises ATMP, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP), and sodium salt, sylvite or ammonium salt etc.Being used for complexing agent of the present invention can be independent kind, perhaps can be two kinds or more kinds of mixtures.
The example of said amino carboxyl salt comprises glycerine, Iminodiacetate, hydroxyethylethylene diamine tri-acetic acid salt, four hydroxyl quadrols, dihydroxymethyl ethylenediamine-N,N'-diacetic acid(EDDA) salt, edetate, ethylenediamine tetrapropionic acid(EDTP) with and sodium salt, sylvite and ammonium salt.
The example that comprises the above-mentioned ethylene diamine derivative of phosphate or its salt or aminocarboxylic acid foundation group or its salt comprises ethylenediamine tetramethylene phosphonic acid; Hydroxyethylethylene diamine tri-acetic acid salt; Four hydroxyl quadrols, methylol ethylenediamine-N,N'-diacetic acid(EDDA) salt, edetate; But preferably with ethylenediamine tetrapropionic acid(EDTP), with and sodium salt, sylvite and ammonium salt as complexing agent of the present invention.
The consumption that is used for complexing agent of the present invention is preferably the 0.005-0.8 mol, more preferably the 0.02-0.6 mol.The mole number of contained complexing agent preferably is equal to or higher than the mole number of contained gold ion in the gold plating liquid.
Electroless gold plating solution of the present invention is included in 1 pyridine carboxylic acid compounds with phenyl or aralkyl.These 1 pyridine carboxylic acid compounds with phenyl or aralkyl makes the tiny gold grain of deposition on as the base metal surfaces of plating subject surface; Form uniform golden plated film; Through the replacement(metathesis)reaction between gold ion and the base metal in the inhibition electroless gold plating solution; Suppress the segregation of base metal, increase deposition of gold speed simultaneously.
1 example with pyridine carboxylic acid compounds of phenyl or aralkyl comprises 1-phenyl-pyridine-2-carboxylic acids, 1-phenyl-pyridine-3-carboxylic acid and 1-phenyl-pyridine-4-carboxylic acid, and 1-phenyl alkylidene group-pyridine carboxylic acid compounds such as 1-benzyl-pyridine-2-carboxylic acids; 1-benzyl-pyridine-3-carboxylic acid, 1-benzyl-pyridine-4-carboxylic acid, 1-(phenyl ether)-pyridine-2-carboxylic acids; 1-(phenylethyl)-pyridine-3-carboxylic acid, 1-(phenyl ether)-pyridine-4-carboxylic acid, 1-(phenyl ether)-pyridine-4-carboxylic acid; 1-(phenyl propyl)-pyridine-2-carboxylic acids, 1-(phenyl propyl)-pyridine-3-carboxylic acid, 1-(phenyl propyl)-pyridine-4-carboxylic acid; 1-(phenyl butyl)-pyridine-2-carboxylic acids, 1-(phenyl butyl)-pyridine-3-carboxylic acid, 1-(phenyl butyl)-pyridine-4-carboxylic acid; 1-(phenylpentyl)-pyridine-2-carboxylic acids, 1-(phenylpentyl)-pyridine-3-carboxylic acid, 1-(phenylpentyl)-pyridine-4-carboxylic acid; And the sodium salt of these carboxylic acids, sylvite or ammonium salt, and the oxyhydroxide of these compounds, muriate and bromide etc.1 a kind of preferred compound with pyridine carboxylic acid compounds of phenyl or aralkyl is 1-benzyl-pyridine-3-carboxylic acid or its carboxylate salt.These compounds can independently use, perhaps can two kinds or more kinds of mixing use.
Being used for 1 consumption with pyridine carboxylic acid compounds of phenyl or aralkyl of the present invention is the 0.1-100 grams per liter, is preferably the 5-30 grams per liter.
Electroless gold plating solution of the present invention preferably also comprises the base metal surfaces treatment agent.Being used for base metal surfaces treatment agent of the present invention is to have the material that the oxidation state metal that is formed at base metal surfaces is carried out the reductive effect, the alloy that said base metal is selected from nickel, copper, cobalt, palladium and comprises these metals.These materials are as reductive agent, with respect to gold ion, and the preferential oxidation base metal; When itself and 1 had the pyridine carboxylic acid compounds blended of phenyl or aralkyl, the corrosion of base metal was suppressed, and tackiness improves; Form uniform golden plated film, deposition of gold speed improves.
The example of these base metal surfaces treatment agents comprises formic acid and salt thereof, like formic acid, and sodium formiate, potassium formiate, ammonium formiate; And hydrazine and verivate thereof, hydrazine for example, Hydrazine Hydrate 80 and hydrazonium sulfate, chlorination hydrazine and salt thereof.Being used for base metal surfaces treatment agent of the present invention can use separately, perhaps can two kinds or more kinds of mixing use.
The consumption that is used for base metal surfaces treatment agent of the present invention is the 0.1-20 grams per liter, is preferably the 1-15 grams per liter.
Electroless gold plating solution of the present invention preferably also comprises poly carboxylic acid or its salt.Said poly carboxylic acid or its salt have suppressed pin hole type corrosion through the surface that is attached to base metal, and can make bath stabilityization with the salt of base metal ion complexation in the plating bath of emanating through forming.The example of this poly carboxylic acid or its salt comprises oxalic acid, toxilic acid, fumaric acid, oxysuccinic acid, Hydrocerol A, hexanodioic acid, and their sodium salt, sylvite or ammonium salt etc.Preferably Hydrocerol A or citric acid tri potassium.Said poly carboxylic acid or its salt can use separately, perhaps two kinds or use more kinds of can mix together.
The consumption that is used for poly carboxylic acid of the present invention or its salt is preferably the 30-75 grams per liter for for example 0-100 grams per liter.
The pH value of electroless gold plating solution of the present invention is preferably 3-8, and more preferably 5 to less than 7.Use the for example pH value of conciliation gold plating liquids of the present invention such as sodium hydroxide, Pottasium Hydroxide, volatile caustic, sulfuric acid, sulfurous acid, HCl, phosphoric acid, cyanic acid, thionamic acid, organic sulfonic acid, phosphonic acids or carboxylic acid.And, if necessary, also the pH stablizer can be provided.The example of pH stablizer comprises phosphoric acid salt, phosphite, borate, carbonate and cyanate etc.
If desired, electroless gold plating solution of the present invention can comprise wetting agent to improve the wettability as the base metal of coating object.Operable wetting agent has no particular limits, as long as said wetting agent is a normally used material in the gold plating liquid.The example of wetting agent comprises non-ionics such as polyoxyalkylene alkyl, polyoxyalkylene alkyl phenyl ether, T 46155 polyoxypropylene glycol, fatty acid polyglycol aklylene glycol, fatty acid polyglycol alkylidene group sorbitanic, and Marlamid; Aniorfic surfactant, fatty acid carboxylate salt for example, AS, sulfonated alkylbenzene; And cationic surfactant, for example alkylamine etc.
If desired, electroless gold plating solution of the present invention also can comprise the gloss of rumbling compound with the golden plated film of further raising, makes golden plated film particle fine and close more.Operable rumbling compound has no particular limits, as long as said rumbling compound is the material that routine is used for gold plating liquid.The example of said rumbling compound comprises thallium, arsenic, lead, copper, antimony etc.Electroless gold plating solution of the present invention can comprise the compound that is different from above-claimed cpd, and the content of these compounds makes them can not cause negative impact to the character of said plating bath.
When using electroless gold plating solution of the present invention to carry out gold-plated the time, said method can be identical with the electroless method of routine.In general, the plating object is immersed in the electroless gold plating solution, can remains on through temperature in the predetermined scope, at nickel, cobalt, copper, palladium or comprise on the surface of base metal of alloy of these metals and form no electric golden plated film plating bath.For example, the bright gold plating liquid of this law can suitably be used as electroless gold plating solution, so as on the metallic surface of nickel or copper and so on deposited gold.
When using electroless gold plating solution of the present invention to carry out gold-plated the time, the temperature of said gold plating liquid (fluid temperature) is 50-100 ℃, is preferably 70 ℃-95 ℃.The plating time is generally 1-60 minute, is preferably 10-30 minute.When using electroless gold plating solution of the present invention to carry out gold-plated the time, said plating bath can mix, exchange and filters or reflux and filter, still especially preferably uses strainer that plating bath is carried out reflux and filter.
Electroless gold plating solution of the present invention has satisfactory stability property, can form the uniform golden plated film with good appearance with the deposition of gold speed that increases, and this gold plated film and base metal have splendid tackiness.And electroless gold plating solution of the present invention has splendid nickel plating thing (when nickel is base metal) grain edges is corroded and the minimized character of pin-hole corrosion.
Embodiment of the present invention is described below, but bright these embodiments that is not limited to of this law.
Embodiment
Embodiment 1-22
For test block; Use known electroless nickel plating solutions (use Ronamax (trade mark) SMT-115 in the electroless nickel plating liquid, it is the product of Rohm And Haas Electronic Mater (Rohm and HaasElectronic Materials Co.Ltd.)) on the copper copper-clad laminate of the patterning of 10 centimetres of 5 cm x, to form thick about 5 microns electroless nickel plated film.
Through in water, adding following component; The electroless gold plating solution that has prepared aqueous solution form: the dicyano potassium aurate of 1.5 grams per liters; The Potssium Cyanide of 50 mg/litre; The ethylenediamine tetramethylene phosphonic acid of 150 grams per liters, the potassium formiate of 10 grams per liters, muriatic 48% the aqueous solution of the 1-benzyl-pyridine-3-carboxylic acid sodium of the Pottasium Hydroxide of 94.3 grams per liters and 0.5 grams per liter.Through other adding Pottasium Hydroxide the pH value of this electroless gold plating solution is adjusted to 5.3.
Above-mentioned test block is immersed in the said electroless gold plating solution 10 minutes under 90 ℃ fluid temperature, form golden plated film.Use the fluorescent X-ray thickness gauge to measure the film thickness of the golden plated film that forms, calculate gold-plated sedimentation rate.In addition, through observing the golden plated film evaluate color and the sedimentary appearance of shortage that forms.The result lists in table 1.
Use gold-plated anti-solution (stripping solution) the Enstrip AU-78M (product of Mei Er Turks Co., Ltd (Meltex Inc.)) that carries to peel off the golden plated film of formation, use FE-SEMJSM-7000F (product of JEOL company) to observe the corrosion that occurs on the nickel surface as base metal.Observations is listed in table 1, and wherein 1=is good, 2=comparatively good (a small amount of corrosion), corrosion that 3=partial corrosion, 4=are comparatively serious and 5=heavy corrosion.
According to preparing electroless gold plating solution with embodiment 1 similar mode, difference is to use the compound of amount shown in the following table 1 to replace comprising the muriatic aqueous solution of 1-benzyl-pyridine-3-carboxylic acid sodium, carries out Electroless plating, observes coating layer.The result lists in table 1.
The gold plating liquid that contains 4-phenyl propyl-pyridine that uses as comparative example 12 can not carry out gold-plated as separation of oil.
As shown in table 1, when use embodiment 1-3 comprise the plating bath of 1-benzyl-pyridine-3-carboxylic acid the time, be suppressed as the corrosion of the nickel plating thing of base metal, deposition of gold speed obviously increases.
The aqueous solution in the table 2 and 3 prepares as electroless gold plating solution.Regulate the pH value of each electroless gold plating solution through other adding Pottasium Hydroxide.Similar with embodiment 1, test block is immersed in the electroless gold plating solution, estimate the outward appearance of the golden plated film that makes and the corrosion that the nickel plated film occurs.The result lists in table 2 and table 3.
According to preparing electroless gold plating solution with embodiment 1 similar mode, difference is the add-on of 1-benzyl-pyridine-3-carboxylic acid, and the pH value of base metal treatment agent and plating bath is as shown in table 5.Solder bonds intensity has also been estimated plating bath stability through following method evaluation.
Embodiment 23
The solder bonds strength test
Carry out remelting (reflow) processing three times to having formed the test block that does not have electric golden plated film on it; The preheating temperature that adds man-hour is 170 ℃; Remelting temperature is 240 ℃, carries out roller under the condition that in following table 4, shows then (bowl mount) is installed, and measures solder bonds intensity.Use ten test blocks to test under various conditions, calculating mean value is as bonding strength.The result lists in table 5.
Table 4
| The pad diameter | 0.50 millimeter |
| Soldered ball | The lead-free solder that diameter is 0.76 millimeter (96.5% tin, 3% silver medal, 0.5% bronze medal) |
| Preheating | 170℃ |
| Remelting | 240 ℃/30 seconds |
| Peak value | 270℃ |
| Solder flux | Sparkle solder flux ES-1061 (Senju metal industry ltd) |
Table 5
The plating bath stability test
100 milliliters of electroless gold plating solutions are poured in the threaded pipe of uncovered, fluid temperature is heated to 90 ℃, heating for some time, separate under these conditions until electroless gold plating solution, so that estimate the stability of this plating bath with water-bath.
Embodiment 24
Through adding following component; Prepared the pH value and be 6.5 the aqueous solution as electroless gold plating solution: 1.5 grams per liter dicyano potassium aurates; 50 mg/litre Potssium Cyanide, 150 grams per liter ethylenediamine tetramethylene phosphonic acids, the hydrazine of 3.5 grams per liters; Muriatic 48% the aqueous solution of the 1-benzyl-pyridine-3-carboxylic acid sodium of 20 grams per liters and the Pottasium Hydroxide of 94.3 grams per liters.
Embodiment 25
According to having prepared electroless gold plating bath with the similar mode of the electroless gold plating bath of embodiment 24, difference is to use 20 gram potassium formiates to replace hydrazine.These plating baths are carried out stability test.The result lists in table 6.
Electroless gold plating solution as routine; Use comprises plating bath (Aurolectroless (trade mark) the SMT-250 electroless gold plating solution that polymine replaces 1-benzyl-pyridine-3-carboxylic acid; Rohm And Haas Electronic Mater's product) also carries out stability test, as comparative example.The result lists in table 6.
Table 6
| Decompose the time opening | Outward appearance | |
| Embodiment 24 | 24 hours | Black precipitate |
| Embodiment 25 | 28 hours | Black precipitate |
| Comparative example 19 | 22 hours | Decompose |
Embodiment 26
The test of poly carboxylic acid effect
Prepared plating bath in the following manner as electroless gold plating solution; Promptly; The aqueous solution that 56 gram citric acid tri potassiums is added following component: the sour potassium of 1.5 grams per liter dicyan funds (I), the Potssium Cyanide of 100 mg/litre, the ethylenediamine tetramethylene phosphonic acid of 150 grams per liters; The hydrazine of 7 grams, muriatic 48% the aqueous solution that comprises 1-benzyl-pyridine-3-carboxylic acid sodium of 20 grams per liters and the Pottasium Hydroxide of 94.3 grams per liters.Through other adding Pottasium Hydroxide the pH value of said electroless gold plating solution is adjusted to 6.5.Use this electroless gold plating solution,, carry out various tests as stated according to having formed golden plated film with embodiment 1 similar mode.
Comprise the gold plating liquid of citric acid tri potassium and compare with the gold plating liquid that does not contain citric acid tri potassium, the former golden coated film deposition speed, golden plated film outward appearance, solder bonds intensity and plating bath stability are significant not different.Yet when use comprised the gold plating liquid of Tripotassium Citrate, the corrosion of the pin hole class of nickel plated film significantly reduced.
Test in the effect of 1 pyridine carboxylic acid compounds with phenyl or aralkyl
As a kind of electroless gold plating solution; Muriatic 48% the aqueous solution of the 1-benzyl-pyridine-3-carboxylic acid sodium shown in the following table 6 is added in the aqueous solution that makes in the following manner: with the sour potassium of dicyan fund (I) of 2 grams per liters; The citric acid tri potassium of the edetate of 45 grams per liters and 67.5 grams per liters adds in the entry, and said pH value of aqueous solution uses Pottasium Hydroxide to regulate.
The test block that uses among the embodiment 1 is immersed in the electroless gold plating solution 10 minutes, 85 ℃ of fluid temperatures, thus form golden plated film.Use the gold-plated anti-counter golden plated film of proposing formation of solution E nstrip AU-78M (product of Mei Er Turks Co., Ltd (Meltex Inc.)) of carrying, use FE-SEMJSM-7000F (product of JEOL company) to observe the corrosion that occurs on the nickel surface as base metal.Observations is listed in table 7, and wherein 1=is good, 2=comparatively good (a small amount of corrosion), corrosion that 3=partial corrosion, 4=are comparatively serious and 5=heavy corrosion.
Table 7
| The amount that adds | pH | The corrosion of nickel plated film | |
| Comparative example 20 | 0 | 5.5 | 5 |
| Embodiment 27 | 10 | 5.5 | 3 |
| Embodiment 28 | 20 | 5.5 | 3 |
| Embodiment 29 | 30 | 5.5 | 3 |
| Embodiment 30 | 40 | 5.5 | 3 |
| Embodiment 31 | 20 | 5.0 | 3 |
Proof has reduced the pin hole class corrosion of nickel plated film through in electroless gold plating solution, adding the muriate of 1-benzyl-pyridine-3-carboxylic acid sodium.
Claims (9)
1. one kind is used for the electroless gold plating solution of in the metallic surface enterprising row metal plating, and it comprises:
(i) the water-soluble gold tricyanide compound of 0.1-10 grams per liter;
The (ii) complexing agent of 0.005-0.8 mol;
(iii) the 0.1-100 grams per liter is selected from 1 at least a compound with pyridine carboxylic acid compounds of phenyl or aralkyl.
2. electroless gold plating solution as claimed in claim 1, it also comprises
(iv) as at least a compound of base metal surfaces treatment agent, it is selected from formic acid and salt thereof, and hydrazine and verivate thereof.
3. electroless gold plating solution as claimed in claim 2 is characterized in that, said base metal surfaces treatment agent is the compound that is selected from hydrazine and verivate thereof.
4. electroless gold plating solution as claimed in claim 1 is characterized in that, said complexing agent is at least a compound that is selected from the ethylene diamine derivative with phosphate or its salt or aminocarboxylic acidic group or its salt.
5. electroless gold plating solution as claimed in claim 1 is characterized in that, said 1 pyridine carboxylic acid compounds with phenyl or aralkyl is at least a compound that is selected from 1-phenyl aryl alkylene-pyridine carboxylic acid compounds.
6. electroless gold plating solution as claimed in claim 2 is characterized in that, this electroless gold plating solution also comprises and (v) is selected from least a compound of poly carboxylic acid and salt thereof.
7. be used on the surface of nickel or copper, carrying out gold-plated electroless gold plating solution, it comprises:
(i) water-soluble gold tricyanide compound;
(ii) complexing agent comprises at least a compound that is selected from the ethylenediamine tetramethylene phosphonic acid or derivatives thereof;
(iii) be selected from 1 at least a compound with pyridine carboxylic acid compounds of phenyl or aralkyl;
(iv) as at least a compound of base metal surfaces treatment agent, it is selected from hydrazine and verivate thereof;
(v) be selected from least a compound of poly carboxylic acid and salt thereof.
8. electroless gold plating solution as claimed in claim 7 is characterized in that, said 1 pyridine carboxylic acid compounds with phenyl or aralkyl is 1-benzyl-pyridine-3-carboxylic acid or its carboxylate salt.
9. electroless gold plating solution as claimed in claim 7 is characterized in that, the pH value of said electroless gold plating solution is more than or equal to 5 and less than 7.
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| CN101845625B (en) | 2010-06-01 | 2012-03-21 | 无锡阿尔法电子科技有限公司 | Method for chemically plating gold on surface of capacitive touch screen |
| KR102482321B1 (en) * | 2014-09-04 | 2022-12-27 | 니혼 고쥰도가가쿠 가부시키가이샤 | Palladium plating solution and palladium coating obtained using same |
| JP6594077B2 (en) * | 2015-07-28 | 2019-10-23 | 上村工業株式会社 | Non-cyanide electroless gold plating bath and electroless gold plating method |
| EP3712298A4 (en) * | 2017-11-16 | 2021-08-11 | JX Nippon Mining & Metals Corporation | Semiconductor substrate and manufacturing method therefor |
| CN113005437B (en) * | 2021-02-24 | 2021-12-24 | 深圳市创智成功科技有限公司 | Chemical gold-precipitating liquid for printed circuit board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687557A (en) * | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| CN1407132A (en) * | 2001-07-02 | 2003-04-02 | 希普雷公司 | Nonelectrolytic gold plating liquid and method thereof |
| CN1435510A (en) * | 2002-01-30 | 2003-08-13 | 关东化学株式会社 | Non-electrolysis gold plating solution |
-
2008
- 2008-07-24 CN CN2008101301265A patent/CN101634021B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687557A (en) * | 1985-03-01 | 1987-08-18 | Heinz Emmenegger | Gold alloys and galvanic bath for the electrolytic deposit thereof |
| CN1407132A (en) * | 2001-07-02 | 2003-04-02 | 希普雷公司 | Nonelectrolytic gold plating liquid and method thereof |
| CN1435510A (en) * | 2002-01-30 | 2003-08-13 | 关东化学株式会社 | Non-electrolysis gold plating solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101634021A (en) | 2010-01-27 |
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